Solutions of polypyrrolidone in aqueous phytic acid and process for making same



c 2,980,641 Patented Apr. 18, 1961 SOLUTIONS OF POLYPYRROLIDONE IN AQUE- OUS PHYTIC ACID AND PROCESS FOR MAK- ING SAME Paul R. Cox, Jr., pecatur, Alta, assignor to The Chemstrand Corporation, Decatur, Ala., a corporation of Delaware No Drawing. Filed Sept. 25, 1958, Ser. No. 763,198 15 Claims. (Cl. 260-292) This invention relates to new compositions of matter. More particularly, the invention relates to new compositions of matter comprising polypyrrolidone and solvents therefor.

Polypyrrolidone possesses many excellent properties which make it desirable for utilization in the manufacture of end products, such as ribbons, films, fibers, filaments, rods,'bristles, lacquers, coatings, shaped articles and the like. Polypyrrolidone can be converted into shaped articles in many ways. For example, it may be cast into films or forced through multi-hole spinnerets to form fibers or filaments. Regardless of the end use to which the polypyrrolidone is to be put, it is generally more convenient and efficient to employ the polymer in a solution. This is well illustrated in the textile industry where polypyrrolidone is employed in the formation of fibers and filaments, which are manufactured by several methods of spinning, such as melt spinning, dry spinning, and wet spinning.

In the melt spinning method, the polymer is heated to a high temperature until it becomes molten and is thereafter forced through sand packs and the like, and thence through a spinneret from which it is extruded in filamentary form. This method has, however, many disadvantages, although it is widely used in the industry at the present time in the production of synthetic fibers and filaments. The high temperatures used in melt spinning require the exercise of extreme care in order to prevent decomposition of the polymer. Furthermore, the high temperatures also affect the chemical and physical characteristics of the polymer and thereby result in a product of inferior quality. In addition to these disadvantages, it is extremely difficult to add to the molten polymer at such high temperatures compounds such as dyes, antistatic agents, plasticizers and the like.

In the dry spinning method of fiber formation, the polymer is dissolved in a suitable solvent and subsequently extruded from a spinneret into a heated atmosphere in order to evaporate the polymer. Even this method, however, has its disadvantages, since during the period of time in which the solvent evaporates, considerable damage may be inflicted on the fibers because of the high heat necessary to bring about solvent evaporation. Another disadvantage of the dry spinning method, and of the melt spinning method also, is the added cost necessary to maintain such high temperatures needed to manufacture the desired end product. 7

The wet spinning method obviates many of the disadvantages of both melt spinning and dry spinning. In order to form filaments by the wet spinning method, the polymer is dissolved in a suitable solvent and extruded from a spinneret into a coagulating bath capable of leaching the solvent from the fiber. Normally, this method may be carried out at temperatures much lower than either the melt spinning or dry spinning methods. If it is desired to use additives, such as dyes, anti-static agents, fire-retarding agents, plasticizers and the like, in the polymeric solution, they may be incorporated therein without the danger of decomposition or seriously affecting the properties of the end product where the wet spinning method of filamentary formation is employed.- Furthermore, it is much easier to introduce such addi tives into a solution than to introduce them into a molten composition. Then again, solutions are much easier to handle during processing, and in many cases may be stored for long periods of time without a change in physical and chemical properties. It is much easier to cast a film from a solution than to cast it from a molten composition. It is readily apparent, therefore, that solutions of polypyrrolidone present many distinct advantages over molten compositions in the manufacture of end products.

Accordingly, it is a primary object of the present invention to provide new and useful compositions of matter comprising polypyrrolidone. It is another object of the invention to provide solutions of polypyrrolidone. It is a further object of the invention to provide solutions of polypyrrolidone which may be converted into shaped articles, such as ribbons, films, filaments, fibers, rods, bristles, lacquers, coatings and the like. It is still another object of the invention to provide a process for the preparation of polypyrrolidone solutions. Other objects and advantages of the instant invention will be readily apparent from the description thereof which follows hereafter.

In general, the objects of the present invention are accomplished by dissolving polypyrrolidone in aqueous phytic acid or aqueous solutions of the water-soluble alkali metal acid salts, alkaline earth metal acid salts or the mixed alkali and alkaline earth metal acid salts thereof.

The phytic acid compounds utilized in the practice of this invention are normally employed in aqueous solutions. The water is generally present in a range of 5 to 50 percent, based on the total weight of the solvent. However, less than 5 percent or more than 50 percent water may be employed with consequent loss of solvent power and in such cases the water and phytic acid mixture is an excellent plasticizer for polypyrrolidone. It is preferred, however, that the water be employed in a range of 30 to 50 percent, based on the total weight of the solvent.

In addition to the phytic acid itself, the water-soluble alkali metal acid salts, alkaline earth metal acid salts and the mixed acid salts of the alkali metals and alkaline earth metals of phytic acid which are useful as solvents in this invention include lithium acid phytate, potassium acid phytate, sodium acid phytate, strontium acid phytate, calcium acid phytate, magnesium acid phytate, lithium calcium acid phytate, sodium magnesium acid phytate,

sodium potassium acid phytate, lithium strontium acidv phytate, lithium potassium acid phytate, lithium sodium acid phytate, lithium magnesium acid phytate, potassium strontium acid phytate, potassium calcium acid phytate, potassium magnesium acid phytate, sodium strontium acid phytate, sodium calcium acid phytate, calcium strontium acid phytate, magnesium strontium acid phytate, calcium magnesium acid phytate, and the like.

Polypyrrolidone soluble in the solvents of this invention may be prepared by various processes. Generally, however, polymeric pyrrolidone is prepared by polymerizing monomeric pyrrolidone in the presence of a catalyst or a catalyst and activator at temperatures in the range of 70 C. to C. However, since the polymerization reaction proceeds well in the range 20 C. and 70 C., these temperatures are preferred in carrying out a polymerization procedure.

In the preparation of polypyrrolidone, a large number of known catalysts are available to catalyze the polymerization. Amo'ng such catalysts, there may be named the alkali metals, namely, sodium, potassiumand lithium,

as well as the hydrides, hydroxides, oxides and salts of the alkali metals, that is, such salts as sodium, lithium and potassium pyrrolidone. Organic metallic compounds, preferably those which are strongly basic, may also be used as catalysts. Examples of such compounds are lithium, potassium and sodium alkyls and aryls of the alkali metals, such as sodium phenyl. Another suitable catalyst is sodium amide. The alkali hydrides, however, are the preferred catalysts, since a distinct advantage is obtained by their use. Sodium hydride, for example, does not react in the polymerization mixture to form water which, as'is well known, has a deleterious etfect upon pyrrolidone polymerization. Where a waterforming catalyst, such as sodium hydroxide, is employed as a catalyst, all water of reaction must be removed from the reaction mixture by vacuum distillation or other means in order to promote polymerization. Generally, the catalyst may be employed in a rangeof 0.002 to 0.25 chemical equivalents based upon one mole of monomeric pyrrolidone in carrying out a polymerization reaction.

Although polypyrrolidone having acceptable properties can be prepared by using a catalyst alone, it is preferable to employ an activator in conjunction with any of the catalysts mentioned above, since the polymer prepared in the presence of both a catalyst and activator has greatly improved properties over polypyrrolidone prepared in the presence of a catalyst alone. Among the compounds which may be employed as activators, there may be named the acyl compounds, such as acetyl pyrrolidone, acetyl morpholone, and the like; lactones, such as gamma butyrolactone, and the like; alkyl esters of monoand dicarboxylic acids, such as ethyl acetate, ethyl oxalate, and the like; the esters of polyhydric alcohols such as ethylene glycol diacetate, and the like; and nitrogen dioxide and organic nitrites having the general formula:

wherein R is selected from the group consisting of alkyl groups containing 1 to 10 carbon atoms, haloalkyl groups containing 2 to 10 carbon atoms, nitroalkyl groups containing 2 to 10 carbon atoms, aralkyl groups containing 7 to 10 carbon atoms, and alkoxy alkyl groups containing 3 to 12 carbon atoms. Among the nitrites falling into the general formula set out above, there are methyl nitrite, ethyl nitrite, n-propyl nitrite, iso-propyl nitrite, n-butyl nitrite, iso-butyl nitrite, amyl nitrite, iso-amyl nitrite, hexyl nitrite, heptyl nitrite, octyl nitrite, nonyl nitrite, decyl nitrite, and their isomeric forms, and the like; haloalkyl nitrites such as 2,2,2-trichloroethyl nitrite; the dihaloalkyl nitrites, such as 2,2-dichloroethyl nitrite, 2,2-dichloropropyl nitrite, 2,2-dichlorobutyl nitrite, 2,2- dichloroamyl nitrite, 2,2-dichlorol1exyl nitrite, 2,2-dichloroheptyl nitrite, 2,2-dichlorooctyl nitrite, 2 .2-dichlorononyl nitrite, 2,2-dichlorodecyl nitrite, and the like monochloroalkyl nitrites, their isomeric forms, and the like; nitroalkyl nitrites, such as 2-nitroethyl nitrite, 2-nitro propyl nitrite, 2-nitrobutyl nitrite, 2-nitroamyl nitrite, 2- mtrohexyl nitrite, 2-nitroheptyl nitrite,2-nitrooctyl nitrite, 2-nitrononyl nitrite, Z-nitrodecyl nitrite, and their isomeric forms, and the like; aralkyl nitrites, such as benzyl nitrite, Z-methylbenzyl nitrite, 3-methylbenzyl nitrite, 4- rnethylbenzyl nitrite, Z-ethylbenzyl nitrite, 3-ethylbenzyl nitrite, 4-ethylbenzyl nitrite, 2-propylbenzyl nitrite, 3- propylbenzyl nitrite, 4-propylbenzyl nitrite, 2-methyl-3- ethylbenzyl nitrite, 2-methyl-4-ethylbenzyl nitrite, Z-methyl-S-ethylbenzyl nitrite, 2-methyl-6-ethylbenzyl nitrite, 3- methyl-4-ethylbenzyl nitrite, 3-methyl-5-ethylbenzyl .nitrite, 3-methyl-6-ethylbenzyl nitrite, 4-methyl-2-ethylbenzyl nitrite, 4-methyl-3-ethylbenzyl nitrite, 2,3-dimethylbenzyl nitrite, 2,4-dimethylbenzyl nitrite, 2,5-dirnethylbenzyl nitrite, 2,6-dimethylbenzyl nitrite, 3,4-dimethylbenzyl nitrite, 3,5-dimethylbenzyl nitrite, and the like; and alko'xyalkyl nitrites, such as Z-methoxyethyl nitrite, Z-ethoxyethyl nitrite, 2-propoxyethyl nitrite, Z-butoxyethyl nitrite, Z-pentoxyethyl nitrite, 2-hexoxyethyl nitrite,

a 2-heptoxyetbyl nitrite, 2-octoxyethyl nitrite, 2-nonoxyethyl nitrite, Z-decoxyethyl nitrite, and their isomeric forms, and the like.

Another excellent polymerization activator is carbon disulfide. Silicon halides and organic silicon halides having the general formula:

aromatic hydrocarbon radical containing 1 to 10 carbon atoms, a saturated or unsaturated aliphatic or aromatic halogenated hydrocarbon radicals contining l to 18 carbon atoms, and X is a halogen, z is an integer from 1 to 4 inclusive, and y is equal to 4-2, wherein R may be similar or dissimilar radicals, may also be employed to activate polymerization of pyrrolidone. Among the silicon halides and organic silicon halides there may be named tetrachlorosilane, a,fi-dichloroethyltrichlorosilane, bis(chloromethyl)methylchlorosilane, butyltrichlorosilane, ch10romethylmethyldichlorosilane, dichloromethyldimethylchlorosilane, diethyldichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, ethyltrichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, propyltrichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, the iodoand bromo-forms of the above compounds, and many others. The trihalides of phosphorous, aluminum, bismuth and antimony, the tetrahalides of titanium, tin, zirconium and lead, and the pentahalides of antimony and phosphorous are also useful as activators in the polymerization of pyrrolidone. Such compounds include aluminum trichloride, aluminum tribromide, aluminum triiodide, stannic tetrachloride, stannic tetrabromide, lead tetrachloride, zirconium tetrachloride, bismuth trichloride, bismuth tribromide, antimony trichloride, antimony tribromide, antimony triiodide, antimony pentachloride, antimony pentaiodide, antimony pentafluoride, and the like. The phosphorous halides include phosphorous tribromide, phosphorous pentabromide, phosphorous trichloride, phosphorous pentachloride, phosphorous trifluoride, phosphorous pentafluoride, r phosphorous triiodide, and the like. Generally,in the preparation of polypyrrolidone wherein both a catalyst and activator are employed to bring about polymerization, the activator is utilized in a range of 0.0001 to 0.075 chemical equivalents of activator, based upon one mole of monomeric pyrrolidone.

The polypyrrolidone soluble in the solvents of this invention is prepared by simple polymerization methods. It can be prepared readily by well-known solution, emulsion, suspension or bulk polymerization procedures; The solution and emulsion polymerizations may be either batch, semi-continuous or continuous methods. When solution polymerization is employed, the monomer is'dissolved in a solvent such as 1,4-dioxane, the desired catalyst or activator, or both, added to the solution and the polymerization carried out under the proper conditions. Well-known solution polymerization apparatus is suitable for preparing the polypyrrolidones described herein. Where either emulsion or suspension polymerization techniques are employed to prepare the polymer, the monomer containing the catalyst is dispersed in a known solvent, such as petroleum ether, and an emulsifying agent then added to the dispersion. Subsequently, the desired activator is injected into the mixture and the dispersion is polymerized until the reaction is complete. At

this time, suitable coagulant is added to the polymerization mixture in order to precipitate the polymer. A'suitable emulsifying agent is sodium lauryl sulfate, and a suitable coagulant is phosphorous acid. When batch polymerization methods are employed in preparing 'polypyrrolidone, no diluent is necessary.

Polypyrrolidone prepared in accordancewiththe procedures set forth hereinabove has a melting point of about 260 C. and .a specific viscosity of .from about 0.3 to 4.5 or more. Itis thus particularly adapted .for :the menu ifacture ofj shaped articles suchv asfilaments, fibers, films, rods,f bristles," and the like. Lower molecularweight polymers prepared in the same manner are. suitable for the: preparation of coatings or. lacquers. I

When dissolving polypyrrolidone in the solvents of the present invention, it may be employed in varying concentrations: The concentration of the polymer in the solvent depends upon the nature of the polymer, the solvent employed andthe temperature, which in turn afiect'the visc'o'sity of the solution. Normally, when the solution is toli be employed in the manufacture of fibers and filaments, as'n'iu'ch as'50 percent of the polymer, based on the total weight of the solution, may be dissolved in the phytic acid solvents. While it is preferred to employ 20 to 40 percent, based on the total weight of the solution, of the polymer in the solvent when the solution is to be used torljth e'preparation of fibers and filaments, it isto be understood that as little as percent or less and more than 50 percent of. the polypyrrolidone may be dissolved in the solventsv of this invention when the solution is to be; employed for other purposes, such as a coating or a lacquer and the like, or when. lower and higher molecular weight polymers are to be dissolved. The amount iof any specific polymer which can be dissolved in the solvents of this invention will be readily evident to those skilled in the art. a

'IIhe solvents of this invention readily dissolve polypyr rolidone within a'wide range of temperature depending upon. the nature of the polymer, the concentration thereofiin. the solvent; and the nature of the solvent itself. Although temperatures within the range of C. to 120 C. are preferred in bringing about the solution, temperaturesaslow: as 5 C..and ashigh as the boiling point of thelpolymer/solvent mixture may be employed where necessary to, bring about dissolution. Heating of the polymer/solvent mixture is preferably accomplished on a; water, glycerine or oil bath. However, other means may be employed. If desired, agitation or stirring of the mixture may be employed during heating or when a solution is being formed at lowtemperatures, although it is to. be understood that it is not always necessary'or critical.

.H Ifiit is desired to produce shapedi articles from the polypyrrolidone. compositions of the present invention which have .a. modified appearance and modified properties, various agents to accomplish these eifects may be added to the polymer solutions priorto fabrication of the articles without having any ill etfectsthereon. Such addedw agents may' b alastiei zers, pigments, dyes, anti-static. agents, fire-retarding agents, and, the like. 5 1

following; examples are intendedto illustratethe new compositions; of this invention more 'fully but are nob-intended. to; limitthe scope of the invention, for'it i sjpossible to effect many modifications therein. In the examples, all parts andpercents are by weight unless Qtherwiseindicated; i

- Exai11pl I- pletedj056 gram- (00029.5 mole) of titanium tetraehlolide wasaddedgtojhe. reaction mixture. This mixwas stoppered,.toiprdtect'v itagainst the atmosphere- ;amd'was'permittedg to stand for hours atjabout 25 C. a Zfihej= polymer recovered by breaking up the cake,

a Wil'e'ytnillp and Washing thepowder,-' "with acetirt le; in' a Wa ring Blender.

' rrae blyiaer was subsequently" air-driedjto constant weight. The polymer had ,aspecific viscosity of;-0.7 6'1 @(Qlet'eiiii dd 0.5 percent solutions, of the polyineriu-QQ hydroxide solution.

mixed and 0.50 part of" the polypyrrolidone prepared above; The mixturewas heated at- C. on a glycerine bath for- 1 /2; hours with occasional stirring. The solution formed was clear, slightly viscous, and stableat 25 C. Fibers drawn therefrom were washed in 25 percent aqueous sodium; hydroxide solution. These fibers were cold drawable and had good tensile strength. A clear film was made from the solution by dipping a glass rod, coated with thesolution, into a bath containingZS percent aqueoussodiumhydroxide.

Example II To a 25 gram (0.294 mole) sample of essentially anhydrous pyrrolidone, there was added under a nitrogen atmosphere 0.75 gram (0.0315 mole) of sodium hydride catalyst. When the evolution of hydrogen gas was completed, 039 gram (0.00293 mole) of anhydrous aluminum chloride was added to the reaction mixture. This mixture was stoppered to protect it against the atmosphere and permitted to standfor 25 hours at about 25 C.v .The polymer was recovered as in the foregoing example and had a specific viscosity, determined on 0.5 percent solutionsof the polymer in 90 percentformic acid at 25 C., of 3.9114.

Subsequently, 2.0 parts of the polypyrrolidone so prepared were mixed with 4L0' parts of phytic acid and 4.0 parts of water. This mixture was heated at C. on a glycerine bath for 3 /2 hours with occasional stirring; The solution; formed was clear, slightly viscous, and stable at 25 C. However, the mixture. became somewhat cloudy at this temperature. Fibers drawn therefrom Were washed in 25 percent sodium hydroxide solution. These. fibers. were cold 'drawable and had good tensile strength. vA clear film was obtained from the solution by submersing a glass rod, coated with the solution into a bath containing 25 percent sodium hydroxide solution.

' j Example III 5.25 parts of phyt'ic' acid and 2.25 parts of water thereafter subme'rsing .the' rod covered with the solution in a bath containing 15 percent aqueous sodium 7 7 Example I V To a 25 gram 0.294 mole) sample of essentially an; hydrous pyrrolidone, there wasiadded under a nitrogen atmosphere075 gram (0.0315 mole) of sodium hydride on a glycerine'ibath at 6'0' C.--for 45 minutes with o e The solution formed was clear and slightly'viscousj ItwasYstable at 25 C. Fibers drawn, therefro'rnwere washed in l 5. percent aqueouss'odiurn. hyf cfat alyst. When the evolution'of hydrogen gas was'cornpleted, 0.7 8 gram (0.00298 mole) of stannic chloride was added to" thjejTre-action'mixture. This mixture was, stopperedto protect it against theatmosphere and was permitted to stand for 25 hours at about 25 CQ polymer was recovered'as in Example I and had a specific viscosity or 4372', determined on 0.5: percent solutions of the polymer'in '90 percent. formic acid at 25 C. I

6.65 parts, of phyti'ev acid and 2".85parts of waterwere 1 mixedjwithfOJO part of. the polypyrrolidone prepared byithe procedure herein'abov'e The mixture washea'tjed casional stirring.

. droxide solutions These fibers. wererc'old"drawableiiand had good tensile strength.- A'filni wasmadeby dippinggl-asjsxrodeovered with thes'olution into'a bath .6611.- tairiing F15 percen aqueous sodium-hydroxide solution- Example V 8.55 parts of phytic acid and 0.95 part of water were mixed with 0.50 part of the polypyrrolidone prepared in Example I. The mixture was heated on a glycerine bath at 90 C. for 1 hour. The solution was clear, slightly viscous and stable at temperatures of 25 C. Fibers drawn therefrom were washed in 15 percent aqueous soduim hydroxide solution. These fibers were cold drawable and had good tensile strength. A film was made by submersing a glass rod coated with the solution into a bath containing 15 percent aqueous sodium hydroxide solution. The film was clear and strong.

Example Vl To a 25 gram (0.294 mole) sample of essentially anhydrous pyrrolidone, there was added under a nitrogen atmosphere 0.75 gram (0.0315 mole) of sodium hydride catalyst. When theevolution of hydrogen gas was completed, 0.88 gram (0.00294 mole) of antimony pentachloride was added to the reaction mixture. The mixture was stoppered to protect it against the atmosphere and was permitted to stand for 25 hours at about 25 C. The polymer was recovered by the procedure disclosed in the foregoing examples and had a specific viscosity of 3.024, determined on 0.5 percent solutions of the polymer in 90 percent formic acid at 25 C.

4.75 parts of calcium acidphytate and 4.75 parts of Water were mixed with 0.50 part of the polypyrrolidone prepared in accordance with the. above procedure. The mixture was heated on a glycerine bath at 73 C. for 45 minutes with occasional stirring. The solution formed was clear, viscous, and stable at 25 C. Fibers drawn therefrom were washed in 15 percent aqueous sodium hydroxide solution. These fibers were cold drawable and had good tensile strength. A film was obtained by dipping a glass rod covered with the polymer solution into a bath containing 15 percent aqueous sodium hydroxide solution. The film .was clear and had good strength.

Example Vll sodium hydroxidesolution. These fibers were cold drawable and had good tensile strength. A clear film was made from thesolution by dipping a glass rodrcoated therewith into a. bath containing 15 percent aqueous sodium hydroxide solution. The film was clear and had good strength.

Example 111 4. 75 parts of calcium acid-phytate andf4.75 parts of water were precooled to C. and mixedwith 0.50 part of the polypyrrolidone prepared in accordance with the procedure of-Example -II., The mixture went into, solution with occasional stirring at a temperatureina range of 5 to 20. C. in 4 hours. Thesolution was clear, viscous, and stable at temperatures as low as 5? C. Fibers drawn therefrom were washed in 15 percent aqueous sodium hydroxidesolution. These fibers were colddrawable and had good tensile strength; Aclea'r filr'n was madeby dipping a glass rod coated with. the solution into a bath containing 15 percent aqueous sodium hydroxide solution. a Q Example 1X 7,

6.65 parts of phytic acid and 2.85 parts; of water were precooled LO-5 C. and mixed with 0.50 par tjof the polypy rrolidoneprepared in accordance withthe procedure in 4 hours. The solution was clear, viscous and stable at temperatures as low as 5 C. Fibers drawn therefrom were washed in 15 percent aqueous sodium hydroxide solution. These fibers'were fcold drawable and had good tensile strength. A clear film was made by dipping a glassrod coated with the solution into abath containing 15 percent aqueous sodium hydroxide solution,

The new compositions of this invention present many advantages. For example, solutions of polypyrrolidone may. be easily prepared on existing equipmentywithout detailed and elaborate procedures. The phytic acid solvents of this invention are inexpensive and readily available. Furthermore, the new solvents of this inven tion are entirely harmless, since they are neither toxic nor explosive and, therefore, may be employed without extraordinary precaution. Polymeric solutions made with the new solvents of this invention are clear and colorless, and products or shaped articles prepared from such solutions exhibit superiorcolor characteristics. to these advantages, the solvents of this invention are further advantageous in that they have noeftect upon the desirable chemical and physical properties of thepolymers dissolved therein. Numerous other advantages of the new compositions of this inventionwill be readily apparent to those skilled in the art.

It will be understood to those skilled in the art that many apparently widely different embodiments of this invention can be made without departing from the spirit and scope thereof. Accordingly, it is to be understood that this invention is not to be limitedto the specific embodiments thereof except asdefined in the appended claims.

I claim: r

l. A new, composition of matter comprising polypyrrolidone dissolved in a solvent containing 5 to 50 percent by weight of water, based on the total weight of the s lvent, and 95 to 50 percent of a compound selected from the group consisting of phytic acid, the watersoluble alkali metal acid salts of phytic acid, the alkaline earth metal acid salts of'phytic acid, and the mixed alkali and alkaline earth metal acid salts of phytic acid. 2. A new composition of matter as defined in claim 1 wherein the solvent contains phytic acid. 4

' 3. A newcomposition of matteras defined in claim 1 wherein the solvent contains calciumacid phytate. 4. 'A new composition of matter as defined in claim 1 wherein the solvent contains sodium acid phytate.

5. A new composition of matter as defined in claim'l wherein the solvent contains magnesium acid phytate.

6. A new composition of matter asdefined in "clairn 1 wherein the solvent contains potassium acid phytatei of Example'VL The mixture went into solutionwith occa-" sional stirrin'g'at a temperature in a range-of 5 to :20? C.

7.A new composition of matter."conipri sing 5 i050 percent, based on the total'weig'ht ot: the composition iof polypyrrolidone dissolved .i'n'a' solvent containing S tQ 50 percent by weight of watenbased on the totalw cight of the solvent, and '95 to '50 percent of ;a' con 1pound selected from the group consisting ofph tic acid, the

water-soluble alkali metal acid salts of phytic acid, the.

alkaline earth metal acid salts otphytic acid andthe mixed alkali and alkaline earth'metal acid salts of phytic .A r V V. v V I 8. A new fiber'forming composition ofmatte r com prising 20 to 40 percent, based on the total weightofthe composition, of polypyrrolidone, having a specific cosity of atleast 0.3, dissolved in a solvent'containing 30 to 50 percent byweig'htaof water, based "on the total weight of the solvent, and to 50 percent of ia com-,

pound selected from .the groupconsisting'of phytic acid;

the water-soluble alkali metal acid salts ofqphyticfacid,

the alkaline earth metal; acid 'saltsoi phytic; acid,}and the mixed alkali and alkaline earth metal-acidisaltsyoi phytic acid.*- s

9. A process lfor preparing. a newr composition, matter comprising mixing polypyrrolidoneand a solvent containing 5 to50 percent byweight of water, based on In addition 9 the total weight of the solvent, and 95 to 50 percent of a compound selected from the group consisting of phytic acid, the water-soluble alkali metal acid salts of phytic acid, the alkaline earth metal acid salts of phytic acid, and the mixed alkali and alkaline earth metal acid salts of phytic acid, and subjecting the mixture to a temperature in a range of 5 C. to the boiling point of the mixture to form a homogeneous solution.

10. The process as defined in claim 9 wherein the solvent contains phytic acid.

11. The process as defined in claim 9 wherein the solvent contains calcium acid phytate.

12. The process as defined in claim 9 wherein the solvent contains sodium acid phytate.

13. The process as defined in claim 9 wherein the 15 2,

solvent contains magnesium acid phytate.

14. The process as defined in claim 9 wherein the solvent contains potassium acid phytate.

15. A process 'for preparing a new fiberforming composition of matter comprising mixing 30 percent, based on the total weight of the composition, of polypyrrolidonc, having a specific viscosity of 3.914, and a solvent containing 50 percent of phytic acid and 50 percent of water, based on the total weight of the solvent, and heating the mixture to a temperature of 107 C. to form a homogeneous solution.

References Cited in the file of this patent UNITED STATES PATENTS Ney et al. May 12, 1953 2,734,004 Robinson Feb. 7, 1956 

1. A NEW COMPOSITION OF MATTER COMPRISING POLYPYRROLIDONE DISSOLVED IN A SOLVENT CONTAINING 5 TO 50 PERCENT BY WEIGHT OF WATER, BASED ON THE TOTAL WEIGHT OF THE SOLVENT, AND 95 TO 50 PERCENT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF PHYTIC ACID, THE WATERSOLUBLE ALKALI METAL ACID SALTS OF PHYTIC ACID, THE ALKALINE EARTH METAL ACID SALTS OF PHYTIC ACID, AND THE MIXED ALKALI AND ALKALINE EARTH METAL ACID SALTS OF PHYTIC ACID. 